Nitrophenyl ether herbicides

ABSTRACT

Compounds of the formula: ##STR1## wherein X is hydrogen, halo, trihalomethyl, alkyl, nitro, or cyano; X 1  is hydrogen, halo, or trihalomethyl; X 2  is trihalomethyl or halo; Y is O, S, NH or NR 1  ; R 1  and R 2  are the same or different radicals selected from hydrogen, alkyl, or mononuclear aralkyl; n is 1 to 5, and Z is carboxy, amino, mono- and dialkyl amino and when Z is carboxy, the agronomically acceptable salts, esters, thioesters and amides thereof, and compositions containing these compounds exhibit herbicidal activity.

This is a continuation of copending application Ser. No. 061,559,653filed on Jan. 23, 198, now abandoned, which is a continuation of06/104,598 filed Dec. 17, 1979 now abandoned.

This invention relates to nitrodiphenyl ethers, compositions containingnitrodiphenyl ethers and to methods of controlling weeds.

Diphenyl ethers are known to be effective weed control agents. See forexample U.S. Pat. Nos. 3,928,416; 3,454,392; 3,798,276; 3,873,303;4,001,005; and 4,029,493 among the many patents issued. However, evennow herbicidal effectiveness of a diphenyl ether cannot be predictedknowing only the structures and often quite closely related compoundswill have quite different weed control abilities. See, Advances inAgronomy, Vol. 24, pages 331, 332, 355, 356, 357 and 358, Herbicides,Chemical Degradation and Mode of Action, Kearney and Kaufman, Vol. 2,Dekker, Inc. pages 552-563 and 728-737 and Mode of Action of Herbicides,Ashton and Crafts and also U.S. Pat. Nos. 3,454,392 and 3,776,961. Anideal herbicide should give selective weed control, over the fullgrowing season, with a single administration at low rates ofapplication. It should be able to control all common weeds by killingthem as the seed, the germinating seed, the seedling, and the growingplant. At the same time, the herbicide should be substantiallynon-phytotoxic to the crops to which it is applied and should decomposeor otherwise be dissipated so as not to poison the soil permanently. Theknown diphenyl ether herbicides fall short of these ideals and thus thesearch continues to discover new herbicides which are more selective orwhich complement the known diphenyl ethers.

In accordance with the present invention, there is provided a new classof diphenyl ether herbicides having the following structural formula:##STR2## wherein X is hydrogen, halo, for example, bromo, chloro,fluoro, iodo and the like, trihalomethyl, for example, trifluoromethyland the like, alkyl, for example, lower alkyl of from 1 to 4 carbonatoms, such as methyl, ethyl, and the like, cyano or ntro; X¹ ishydrogen, halo, for example, bromo, chloro, fluoro, iodo and the like,or trihalomethyl, such as trifluoromethyl and the like; X² istrihalomethyl such as trifluoromethyl and the like or halo, such aschloro, bromo, fluoro and the like; Y is O, NH, NR¹ or S; R¹ and R² arethe same or different radicals selected from hydrogen, lower alkyl offrom 1 to 4 carbon atoms, mononuclear aryl lower alkyl, such as benzyl,phenethyl and the like; n is an integer of from 1 to 5 and Z carboxy,amino, mono- and dialkylamino, for example mono- and di loweralkyl-amino such as methylamino, ethylamino, propylamino, butylamino,dimethylamino, diethylamino, dpropylamino, dibutylamino and the like andwhen Z is carboxy the agronomically acceptable salts, esters and amidesthereof. Examples of salts include the alkali metal and alkaline earthmetal salts, such as lithium, sodium, potassium, magnesium and the like.Examples of esters include saturated and unsaturated, substituted andunsubstituted alkyl esters, preferably lower alkyl esters of from 1 to 6carbon atoms, such as the methyl, ethyl, propyl, butyl, tert- butyl,pentyl and hexyl esters wherein the substituents on the alkyl may beselected from alkoxy, for example, lower alkoxy, such as methoxy,ethoxy, propoxy, butoxy and the like, halo-alkoxy, for example, halolower alkoxy such as chloroethoxy, bromoethoxy and the like,trihalomethylalkoxy for example, trifluoromethyl lower alkoxy such astrifluoromethylmethoxy and the like. Also included are unsaturatedesters of from 3 to 5 carbon atoms, for example, allyl, propynyl,α-methylallyl, α-ethylallyl, and the like.

A preferred embodiment of this invention relates to compounds of theformula: ##STR3## wherein R^(1') and R^(2') are selected from hydrogenor lower alkyl; n' is an integer of 1 or 2 and R³ is hydrogen,saturated, unsaturated, substituted or unsubstituted alkyl, for example,saturated, unsaturated, substituted or unsubstituted lower alkyl of from1 to 6 carbon atoms, such as, methyl, ethyl, n-propyl, iso-propyl,n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and the like,unsaturated lower alkyl of from 3 to 5 carbon atoms such as allyl andthe like, trifluoromethyl lower alkyl for example, trfluoromethylmethyland the like, an alkali metal cation for example lithium, sodium,potassium and the like or an alkalne earth metal cation, for example,calcium, magnesium and the like. These compounds exhibit particularlygood herbicidal activity.

Examples of the compounds of the invention embraced by Formula Iinclude:

2-chloro-4-trifluoromethyl-3'-carbomethoxymethoxy-carbonyl-4'-nitrodiphenylether,

2,4,6-trichloro-3'-carbomethoxymethoxycarbonyl-4'nitrodiphenyl ether,

2,4-dichloro-3'-carboxymethoxycarbonyl-4'-nitro-diphenyl ether,

2-chloro-4-trifluoromethyl-3'-sodiocarboxymethoxy-(carbonyl-4'-nitrodiphenylether,

2-fluoro-4,6-dichloro-3'-N(carbomethoxymethyl)-carbamyl-4'-nitrodiphenylether,

2-fluoro-4-trifluoromethyl-3'-(1-carbomethoxy)-propylthiocarbonyl-4'-nitrodiphenylether,

2-fluoro-4-trifluoromethyl-6-chloro-3'-(1-allyloxy-carbonyl)butoxycarbonyl-4'-nitrodiphenylether

2,4,6-trichloro-3'-carbo(2-methoxy)ethoxymethoxy-carbonyl-4'-nitrodiphenylether,

2-bromo-4-trifluoromethyl-3'-(2-carbomethoxy)ethoxyo-carbonyl-4'-nitrodiphenylether,

2-methyl-4-trifluoromethyl-3'-(1-carbomethoxy)phen-ethoxycarbonyl-4'-nitrodiphenylether,

2-cyano-4-trifluoromethyl-3'-w-carbomethoxypentoxy-carbonyl-4'-nitrodiphenylether,

2-nitro-4-chloro-3'-carbotrifluoroethoxymethoxycar-bonyl-4'-nitrodiphenylether,

2-fluoro-4-bromo-3'-carbamylmethoxycarbonyl-4'nitrodiphenyl ether,

2,4,6-trchloro-3'-(1-N-dimethylcarbamyl)phenethoxy-carbonyl-4'-nitrodiphenylether,

4-trifluoro-3'-(1-carbomethoxy)benzyloxycarbonyl-4'nitrodiphenyl ether,

2,4-dichloro-3'-(1-carbomethoxyisopropoxycarbonyl)-4'-nitrodiphenylether

2,4,6-trichloro-3'-(1-carbomethoxysopropoxycarbc onyl)-4'-nitrodiphenylether,

2,4-dichloro-3'-(1-carbomethoxyisobutoxycarbonyl)-4'-nitrodiphenylether,

2-fluoro-4,6-dichloro-3'-(1-carbomethoxyisopropoxy-carbonyl)-4'-nitrodiphenylether,

2,4-dichloro-3'-(1-carbomethoxy-2-phenylethoxycarb-onyl)-4'-nitrodiphenylether,

2,4,6-trichloro-3'-(2-carbomethoxyisopropoxycarb-onyl)-4'-nitrodiphenylether,

2,4-dichloro-3'-(1-methyl-3-carbomethoxypropoxycarb-onyl)-4'-nitrodiphenylether,

2,4,6-trichloro-3'-(3-carbomethoxypropoxycarbonyl)-4'-nitrodiphenylether, and

2,4-dichloro-3'-(4-carbomethoxy-n-butoxycarbonyl)-4'nitrodiphenyl ether.

The products of this invention may be prepared by one of four methodswhich comprises treating an acid halide with an alkoxy substitutedcompound; by treating an alkali metal or alkaline earth metalcarboxylate with a halo substituted compound and where necessarytreating the intermediate with a nitrating agent or by treating analkali metal phenoxide with an appropriately substituted5-halo-2-nitrobenzene.

The first process comprises treating 4-substitutedphenyl-3'-halocarbonyl-4'-nitrophenyl ether (II) with an appropriatecompound in the presence of an inert solvent, such as toluene and thelike, optionally, in the presence of an acid acceptor. The reaction maybe conducted at a temperature in the range of from about 20° to about150° C. for a period of time of from about 15 minutes to about 24 hours;however, the reaction is generally conducted at 30° to 40° C. for aperiod of time of about 2 hours. The following equation illustrates thisprocess: ##STR4## wherein X, X¹, X², Y, R¹, R², n and Z are as definedabove and halo is chloro, bromo and the like.

The second process comprises treating 4-substituted phenyl-3-alkalimetal (or alkaline earth metal) oxycarbonyl-4'-nitrophenyl ether with ahalo substtuted compound in the presence of an inert solvent, such asdimethyl formamide, dimethyl sulfoxide, sulfolane, methylethyl ketone,and the like at a temperature in the range of from about 20° to about150° C. for a period of time in the range of from about 1/4 to about 6hours. The following equation illustrates this process: ##STR5## whereinX, X¹, X"R¹, R², n, z and halo are as defined above and M is a cationderived from an alkali or alkaline earth metal.

The third process comprises treating an appropriately substitutedphenoxide with an appropriately substituted -halo-2-nitrobenzene. Thefollowing equation illustrates this process: ##STR6## wherein X, X¹, X²,Y, R¹, R², n, Z and M are as defined above and halo is chloro, fluoro,bromo and the like. The reaction is generally conducted at a temperaturein the range of from about 50° to about 150° C. for a period of timefrom about 1 to about 96 hours. Solvents which may be employed includedimethyl sulfoxide, dimethyl formamide, sulfolane, methyleethyl ketone,and the like.

Process comprises treating 4-substituted phenyl-3-alkali metal (oralkaline earth metal)oxycarbonyl phenyl ether with a halo substitutedcompound as described in the Second Process, supra, followed bynitration employing as the nitrating agent, nitric acid, nitricacid/sulfuric acid, nitroniumtetrafluoroborate, nitroniumhexafluorophosphate, acetylnitrate and the like. Solvents, if employedinclude sulfolane, acetic anhydride (acetyl nitrate) and the like at atemperature in the range of from about 20° to about 200° C. andpreferably in the range of from about 50° to about 150° C. for a periodof time in the range of from 1/2 hour to 6 hours. The following equationillustrates this process. ##STR7## wherein X, X¹, X², R¹, R², n, Z andhalo are as defined above.

The diphenyl ethers (I, supra) of the invention are useful aspreemergence and postemergence herbicides. Preemergence herbicides areordinarily used to treat the soil by application either before seeding,during seeding, or after seeding and before the crop emerges.Postemergence herbicides are those which are applied after the plantshave emerged and during their growth period. The compounds of thisinvention are especially active as postemergence herbicides.

Among the crops on which the diphenyl ethers of the invention can beadvantageously employed are, cotton, soybeans, peanuts, beans, peas,carrots, corn, wheat, and other cereal crops.

The diphenyl ethers (I, supra) are useful for controlling weeds in ricecrops. When used in transplanted rice crops, the ethers can be appliedeither preemergence or postemergence to the weeds --that is, they can beapplied to the transplanted rice plants and their growth medium eitherbefore the weed p ants have emerged or while they are in their earlystages of growth. The ethers can be applied to the growth medium eitherbefore or after the rice has been transplanted to that medium.

The diphenyl ethers (I, supra) can be applied in any amount which willgive the required control of weeds. A standard rate of application ofthe herbicdes of the invention is in the range from about 0.02 to about12 pounds of diphenyl ether per acre. A preferred range is from about0.1 to about 2 pounds per acre.

Under some conditions, the diphenyl ethers (I, supra) may beadvantageously incorporated into the soil or other growth medium priorto planting a crop. This incorporation can be by any convenient means,including simple mixing with the soil, applying the diphenyl ether tothe surface of the soil and then disking or dragging into the soil tothe desired depth, or by employing a liquid carrier.

The diphenyl ethers of the invention can be applied to the growth mediumor to plants to be treated either neat or as a component in a herbicidalcomposition or formulation which also comprises an agronomicallyacceptable carrier. "Agronomically acceptable carrier" is any carrierwhich can be used to dissolve, disperse or diffuse a herbicidal compoundin the composition without impairing the effectiveness of the herbicidalcompound and which by itself has no permanent detrimental effect on thesoil, equipment, crops, or agronomic environment. Mixtures of thediphenyl ethers of the invention may also be used in any of theseherbicidal formulations. The herbicidal compositions of the inventioncan be either solid or liquid formulations or solutions. For example,the diphenyl ethers can be formulated as wettable powders, emulsifiableconcentrates, dusts, granular formulations, aerosols, or flowableemulsion concentrates. In such formulations, the compounds are extendedwith a liquid or solid carrier and, when desired, suitable surfactantsare incorporated.

It is usually desirable, particularly in post-emergence applications, toinclude adjuvants, such as wetting agents, spreading agents, dispersingagents, stickers, adhesives, and the like, in accordance withagricultural practices. Examples of adjuvants which are commonly used inthe art can be found in the John W. McCutcheon, Inc. publication"Detergents and Emulsifiers 1969 Annual."

Examples of solvents which are useful in the practice of this inventioninclude alcohols, ketones, aromatic hydrocarbons, dimethyl formamide,dioxane, dimethyl sulfoxide, and the like. Mixtures of these solventscan also be used. The concentration of the solution can vary from about2% to about 98% of active product with a preferred range being fromabout 25% to about 75%.

For the preparation of emulsifiable concentrates, the diphenyl ether canbe dissolved in organic solvents, such as benzene, toluene, xylene,methylated naphthalene, corn oil, pine oil, o-dichlorobenzene,isophorone, cyclohexanone, methyl oleate, and the like, or in mixturesof these solvents, together with an emulsifying agent which permitsdispersion in water. Suitable emulsifiers include, ethylene oxidederivatives of alkylphenols or long-chain alcohols, mercaptans,carboxylic acids, and reactive amines and partially esterifiedpolyhydric alcohols. Solvent-soluble sulfates or sulfonates, such as thealkaline earth salts or amine salts of alkylbenzenesulfonates and thefatty alcohol sodium sulfates, having surface-active properties can beused as emulsifiers either alone or in conjunction with an ethyleneoxide reaction product. Flowable emulsion concentrates are formulatedsimilarly to the emulsifiable concentrates and include, in addition tothe above components, water and a stabilizing agent such as awater-soluble cellulose derivative or a water-soluble salt of apolyacrylic acid. The concentration of the active ingredient inemulsifiable concentrates is usually from about 10% to 60% and inflowable emulsion concentrates, can be as high as about 75%.

Wettable powders suitable for spraying, can be prepared by admixing thecompound with a finely divided solid, such as clays, inorganic silicatesand carbonates, and silicas and then incorporating wetting agents,sticking agents, and/or dispersing agents. The concentration of activeingredients in such formulations is usually in the range of from about20% to about 98%, and, preferably, from about 40% to about 75%. Adispersing agent can constitute about 0.5% to about 3% of thecomposition, and a wetting agent can constitute from about 0.1% to about5% of the composition.

Dusts can be prepared by mixing the compounds of the invention withfinely divided inert solids which may be organic or inorganic in nature.Materials useful for this purpose include, for example, botanicalflours, silicas, silicates, carbonates and clays. One convenient methodof preparing a dust is to dilute a wettable powder with a finely dividedcarrier. Dust concentrates containing from about 20% to about 80% of theactive ingredient are commonly made and are subsequently diluted toabout 1% to about 10% use concentration.

Granular formulations can be prepared by impregnating a solid, such asgranular fuller's earth, vermiculite, ground corn cobs, seed hulls,including bran or other grain-hulls, or similar material. A solution ofone or more of the diphenyl ethers in a volatile organic solvent can besprayed or mixed with the granular solid and the solvent then removed byevaporation. The granular material can have any suitable size, with apreferable size range of from 16 to 60 mesh. The diphenyl ether willusually comprise from about 2 to about 15% of the granular formulation.

The diphenyl ethers of the invention can also be mixed with fertilizersor fertilizing materials before their application. In one type of solidfertilizing composition in which the diphenyl ethers can be used,particles of a fertilizer or fertilizing ingredients, such as ammoniumsulfate, ammonium nitrate, or ammonium phosphate, can be coated with oneor more of the ethers. The solid diphenyl ethers and solid fertilizingmaterial can also be admixed in mixing or blending equipment, or theycan be incorporated with fertilizers in granular formulations. Anyrelative proportion of diphenyl ether and fertilizer can be used whichis suitable for the crops and weeds to be treated. The diphenyl etherwill commonly be from about 5% to about 25% of the fertilizingcomposition. These compositions provide fertilizing materials whichpromote the rapid growth of desired plants, and at the same time controlthe growth of undesired plants.

The diphenyl ethers of the invention can be applied as herbicidal spraysby methods commonly employed, such as conventional high-gallonagehydraulic sprays, low-gallonage sprays, airblast spray, aerial spraysand dusts. For low volume applications a solution of the compound isusually used. The dilution and rate of application will usually dependupon such factors as the type of equipment employed, the method ofapplication, the area to be treated and the type and stage ofdevelopment of the weeds.

For some applications, it may be desirable to add one or more otherherbicides along with diphenyl ethers of the invention. Examples ofother herbicides which can be incorporated to provide additionaladvantages and effectiveness include:

Carboxylic Acids and Salts and Ester Derivatives Thereof

2,3,6-trichlorobenzoic acid, 2,3,5,6-tetrachlorobenzoic acid,2-methoxy-3,5,6-trichlorobenzoc acid, 2-methoxy-3,6-dichlorobenzoicacid, 2-methyl-3,6-dichlorobenzoi acid, 2,3-dichloro-6-methylbenzocacid, 2,4-dichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyaceticacid, 2-(2,4,5-trichlorophenoxy)propionic acid,4-(2,4-dichlorophenoxy)butyric acid, 4-(2-methyl-4-chlorophenoxy)butyricacid, 2,3,6-trichlorophenylacetic acid, 3,6-endoxohexahydrophthalicacid, dimethyl 2,3,5,6-tetrachloroterephthalate, trichloroacetic acid,2,2-dichloropropionic acid, 3-amino-2,5-dichlorobenzoic acid,2,3-dichloroisobutyric acid.

Carbamic Acid Derivatives

ethyl N,N-di(n-propyl)thiocarbamate, propyl N,N-di-acid,(n-propyl)thiocarbamate, ethyl N-ethyl-N-(n-butyl)thiocarbamate, ethylN-ethyl-N-(n-butyl)thiocarbamate, propylN-ethyl-N-(n-butyl)thiocarbamate, 2-chloroallylN,N-diethyldithiocarbamate, N-methyldithiocarbamic acid salts, ethyl1-hexamethyleneiminecarbothiolate, isopropyl N-phenylcarbamate,isopropyl N-(m-chlorophenyl)carbamate, 4-chloro-2-butynylN-(m-chlorophenyl)carbamate, methyl N-(3,4-dichlorophenyl)carbamate,methyl-m-hydroxcarb-anilate-m-methylcarbanilate,S-(4-chlorobenzyl)-N,Ndiethylthiolcarbamate.

Phenols

dinitro-o-(sec-butyl)phenol and its salts, pentachlorophenol and itssalts

Substituted Ureas

3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea,3-(3,4-dichlorophenyl)-3-methoxy-1-dimethylene,3-(4-chlorophenyl)-3-methoxy-1,1-dimethylurea,3-(3,4-dichlorophenyl)-1-n-butyl-1-methylurea,3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea, phenyl)-1,1-diethylurea,dichloral urea,N'[4-[2-methylphenyl)ethoxy]phenyl]-N-methoxy-N-methylurea,1,1,3-trimethyl-3-(5-p-chlorobenzylthio-1,3,4-thia-diazol-2-yl)urea,3-[-chlorophenoxy)phenyl]-1,1 -dimethylurea.

Substituted Triazines

2-chloro-4,6-bis(ethylamino)-s-triazine, 2-chloro4-ethylamino-6-isopropylamino-s-triazine,2-chloro-4,6-bis(methoxypropylamino)-s-triazine, 2-methoxy-4,6-bi(isopropylamino)-s-triazine,2-chloro-4-ethylamino-6-(3-methoxypropylamino)-s-triazine,2-methylmercapto-4,6(ethylamino)-s-triazine,2-methylmercapto-4-ethylamno-6-isopropylamino-s-triazine,2-chloro-4,6-bis(isoropyl-amino)-s-triazine,2-methoxy-4,6-bis(ethylamino)-s triazine,2-methoxy-4-ethylamino-6-isopropylamino-triazine,2-methylmercapto-4-(2-methoxyethylamino)-6-isopropylamino-s-triazine.

Diphenyl Ether Derivatives

2,4-dichloro-4'-nitrodiphenyl ether, 2,4,6-tri-Ochlorophenyl ether,2,4-dichloro-6-fluoro-4'-nitrodiphenyl ether2,-chloro-4-trifluoromethyl-3'-carboxy-4'-nitrodiphenyl ether and itssalt and ester derivatives, 3-methyl-4'-nitrodiphenyl ether,3,5-dimethyl-4'-nitrodiphenyl ether,2,4'-dinitro-4-trifluoromethyldiphenyl ether, 2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether, sodium5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoate.

Anilides

N-(3,4-dichlorophenyl)propionamide,N-(3,4-dichlorophenyl)methacrylamide,N-(3-chloro-4-methylphenyl)-2-methylpentanamide,N-(3,4-dichlorophenyl)trimethylacetamide,N-(3,4-dichlorophenyl)-β,β-dimethylvaleramide,N-isopropyl-N-phenylchloroacetamide,N-n-butoxymethyl-N-(2,6-diethylphenyl)chloroacetamide andN-n-methoxy-methyl-N-(2,6-diethylphenyl)chloroacetamide,2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide.

Uracils

5-bromo-3-s-butyl-6-methyluracil,5-bromo-3-cyclo-hexyl-1,6-dimethyluracil,3-cyclohexyl-5,6-trimethylene-uracil, 5-bromo-3-isopropyl-6-methyluraciland 3-tert-butyl-5-chloro-6-methyluracil.

Nitriles

2,6-dichlorobenzonitrile, diphenylacetonitrile,3,5-dibromo-4-hydroxybenzonitrile, and 3,5-diiodo-4-hydroxybenzonitrile.

Other Organic Herbicides

b 2-chloro-N,N-diallylacetamide,N-(1,1-dimethyl-2-propynyl)-3,5-dichlorobenzamide, maleic hydrazide,-amino-1,2,4-triazole, monosodium methanearsonate,N,N-diallyl-2-chloroacetamide, disodium methanearsonate,N,N-dimethyl-β,β-diphenylacetamide,N,N-di(n-propyl)-2,6-4-methylaniline, N,N-di(n-propyl)-2,6-dinitro4-methylsulfonylaniline, N³,N³-di-n-propyl-2,4-dinitro-6-trifluoromethyl-m-phenylenediamine,3,5-dinitro-N⁴, N⁴ -dipropylsulfanilamide,4-isopropyl-2,6-dinitro-N,N-dipropylaniline,N-[2-chloroethyl)-2,6-dinitro-N-propyl-4-trifluoromethylaniline,0-(2,4-dichlorophenyl)-0-methylisopropylphosphoramidothioate,4-amino-3,5,6-trichloropicolinic acid, 2,3-dichloro-1,4-naphthoquinone,di-(methoxythiocarbonyl)disulfide,3-isopropyl-1H-2,1,3-benzothiadiazine(4)3H-one-2,2,diooxide,6,7-dihydrodipyridol-[1,2-a:2',1'-c]pyrazidinium salts,1,1'-dimethyl-4,4'-bi-pyridinium salts and3,4,5,6-tetrahydro-3,5-dimethyl-2-thio-2H-1,3,5-thiadiazine,2-(α-naphthoxy)-N-diethylacetamide, 2-N-(1-napthylaminocarbonyl)benzoicacid, 3-isopropyl-1H-2,1,3-beno-thiadiazin-4(3H)-one 2,2-dioxide,methyl-2-4-(4-chlorophe propionate,methyl-2-4-(3,5-dichloro-pyrid-2-yl)phenoxy]propionate,2-[1-(allyloxyamino)propylidene]4-carbomethoxy-5,5-dimethylcylohexane-1,3-dione.

When mixtures of herbicides are employed, the relative proportions whichare used will depend upon the crop to be treated and the degree ofselectivity in weed control desired.

EXAMPLE 12-Chloro-4-trifluoromethyl-3'-(carbo-tert-butoxycarbonyl-methoxycarbonyl)-4'-nitrodiphenylether

2-Chloro-4-trifluoromethyl-3-carboxy-4'-nitrodiphenyl ether (46.2 grams;0.128 moles) is dissolved in dimethyl sulfoxide (100 ml.) Potassiumcarbonate (17.7 grams; 0.128 moles) is added and the reaction mixtureheated with stirring to 60° C. The reaction mixture is then cooled to15° C. and allowed to warm to room temperature. Tert-butyl bromoacetateis then added and the reaction mixture stirred at room temperature forone hour. The reaction is repeated substantially as stated above and thetwo reactions combined and diluted with ether, the ether extract iswashed with water then 1% sodium hydroxide solution and finally 5%sulfuric acid solution. The ether solution is then dried over magnesiumsulfate. The ether solution is filtered through activated silica gel andthe ether evaporated to afford 104.8 grams of2-chloro-4-trifluoromethyl-3'-(carbo-tert-butoxy-methoxycarbonyl)-4'-nitrodiphenylether which after recrystallization from hexane at 0° C. had a m.p. of25° C. Elemental analysis: Found C, 50.13; H, 3.51; N, 2.87; Cl, 7.38;F, 12.30. C₂₀ H₁₇ ClF₃ NO₇ requires C, 50.49; H, 3.60; N 2,94; Cl, 7.45;F, 11.98.

EXAMPLE 2 2-Chloro-4-trifluoromethyl-3'-(carboxymethoxycarbonyl)4'-nitrodiphenyl ether

2-Chloro-4-trifluoromethyl-3'-tert-butoxycarbonyl-methoxycarbonyl-b4'-nitrodiphenyl ether (12.0 grams) is heated in an oil bath to 165° C.until bubbling ceased. The product is dissolved in ether, extracted into5% potassium carbonate, the extract acidified with 5% sulfuric acid andextracted with ether. The ether extract is dried over magnesium sulfatefiltered through activated silica gel and the ether removed to afford9.9 grams of 2-chloro-4-trifluoromethyl-3'(carboxymethoxycarbonyl)-4'-nitrodiphenyl ether. Alater sample crystallized and was recrystallized from toluene/hexane,m.p. 103.5°-106° C. Found, 45.99; H, 2.59; N, 2.88; Cl, 8.00; F, 13.02;C₁₆ H₇ ClF₃ NO₇ requires C, 45.79; H, 2.16; N, 3.34; C1, 8.45; F, 13.58.

EXAMPLE 32,4-Dichloro-3'-(tert-butoxycarbony1methoxycarbonyl)-4'-nitrodiphenylether

A mixture of 2,4-dichloro-3'-carboxy-4'-nitrodiphenyl ether (20.7grams), potassium carbonate (9.7 grams) and dimethyl sulfoxide (30 ml.)is heated to 50° C. for 10 minutes and then cooled to 30° C. Tert-butylbromoacetate is then added followed by an additional 5 m, of dimethylsulfoxide. The temperature of the reaction mixture rises to 35° C. andthe mixture turns yellow. The reaction mixture is stirred for one hourand let stand overnight at room temperature. The reaction mixture ispoured into water and extracted with 300 ml. of diethyl ether. The ethersolution is washed with water and then with 5% sulfuric acid and thenwith 5% sodium hydroxde. The ether solution is dried over magnesiumsulfate and filtered. Removal of the ether affords 15 grams of theyellow-green oil which is dissolved at hot hexane and allowed tocrystallize. Filtration affords 10.5 grams of2,4-dichloro-3'-(tert-butoxycarbonylmethoxycarbonyl)-4'-nitrodiphenylether as yellow-white crystals, melting point 69°- 72° C.

EXAMPLE 4 2,4-Dichloro-3'-(carboxymethoxycarbonyl)-4'-nitrodiphenylether

2,4'Dichloro-3'-(tert-butoxycarbonylmethoxycarbonyl)-4'-nitrodiphenylether (16 grams) is heated at 160°-170° 90 minutes to afford a veryviscous fluid orange-brown in color. The product is extracted withdiethyl ether (200 ml.) and washed with potassium carbonate solution.The aqueous phase is acidified with 5% sulfuric acid and extracted withether. The ether solution is dried, filtered and the ether removed toafford 13.4 grams of crude product as a yellow oil. This material wasdissolved in 200 cc's of carbon tetrachloride and hexane and allowed tocool. Filtration afforded 11.9 grams of substantially pure2,4-dichloro-3'-(carboxymethoxy-4'-nitrodiphenyl ether, melting point93°-95° C. Infrared spectral analysis and NMR analysis confirm thestructure.

EXAMPLE 52-Chloro-4-trifluoromethyl-3'-(1-carbomethoxyethoxy-carbonyl)-4'-nitrodiphenylether

2-Chloro-4-trifluoromethyl-3'-carboxy-4'-nitrodiphenyl ether (10.0grams; 0.028 moles) is dissolved in methylethyl ketone (150 ml.) andpotassium carbonate (3.9 grams; 0.028 moles) is added. The solution isheated with stirring to reflux and a white solid preciptates. Thesolution is cooled to room temperature and methyl bromopropionate isadded. The reaction mixture is heated to 75° C. for approximately 3hours. (Note that during this period an additional one gram of methylbromopropionate had been added.) The reaction mixture is diluted withether and the aqueous layers separated and discarded. The ether extractis washed with 5% sulfuric acid and then 1% sodium hydroxide solution.The ether is dried with magnesium sulfate, filtered through silica geland the ether removed to afford 8.3 grams of2-chloro-4-trifluoro-methyl-3-(1-carbomethoxyethoxycarbonyl)-4'-nitether as an oil.

EXAMPLE 62-Chloro-4-trifluoromethyl-3'-[1-(carboethoxy)ethoxy-carbonyl]-4'-nitrodiphenylether

To a solution of2-chloro-4-trifluoromethyl-3'-chlorocarbonyl-4'-nitrophenyl ether (9.0grams; 0.0236 mole) in 1,2-dimethoxyethane (25 ml.) in a 50 ml. roundbottom flask is added ethyl lactate (2.8 grams; 0.0236 moles) at roomtemperature. Pyridine (1.58 grams; 0.0236 mole) is also added. Thereaction mixture is stirred over the weekend at room temperature, andthen heated to 75° C. for about 24 hours. The reaction mixture isfiltered to remove solid and the filtrate concentrated to afford 12grams of a yellow oil. The yellow oil is chromatographed over 100 gramsof silica gel using toluene as the solvent to give 3.5 g of2-chloro-4-trifluoromethyl-3'-(1-carboethoxy)ethoxycarbonyl-4'-ntrodiphenyletheras yellow oil of 74% purity contaminated with a second product.

EXAMPLE 72-Chloro-4-trifluoromethylphenyl-3'-2[(N,N-dimethylamno)ethoxycarbonyl]-4'-nitrophenylether Step A - Potassium 2-chloro-4-trif1uoromethyl-phenoxide

2-Chloro-4-trifluoromethylphenol (1.96 grams; 0.010 mole) is dissolvedin dimethyl sulfoxide (15 ml.) and The reaction mixture is stirred atroom temperature overnight to afford potassium2-chloro-4-trif1uoromethylphenoxide.

Step B -2-Chloro-4-trifluoromethylphenyl-3'-2[(N,N-dimethylamino)ethoxycarbonyl)-4'-nitrophenylether

To the product of Step A is added5-fluoro-2-nitro-(N,N-dimethylaminoethoxycarbonyl)benzene. The reactionmixture is stirred at room temperature for 3 hours and then warmed to45° for about 18 hours. The reaction mixture is poured into carbontetrachloride (100 ml.) and extracted with two portions of water (2×50ml.). The carbon tetrachloride layer is dried over anhydrous sodiumsulfate, filtered and the solvent removed under vacuum to afford 2.8grams of2-chloro-4-trif1uoromethylphenyl-3'-2-[(N,N-dimethylamino)ethoxycarbonyl)-4'-nitrophenylether. Recrystallization from benzene/hexane afforded substantially pureproduct having a melting point of 70°-71.5° C. Elemental analysis for:Found C, 48.94, H, 3.74 N, 6.18 Cl, 8.14 F, 13.58 C₁₈ H₁₆ HlF₃ N₂ O₅requires C, 49,95 H, 3.73 N, 6.47 Cl, 8.19 F, 13.14

In a manner similar to that described in Examples 1 or 5 all of thediphenyl ethers of this invention may be obtained. Thus by substitutingthe appropriately substituted halo compound or hydroxy compound for thetert-butyl bromoacetate or ethyl lactate of Examples 1 and 5,respectively, and by following substantially the procedures described inExamples 1 and 5, respectively, the diphenyl ether products of thisinvention may be obtained. The following equation illustrates thereaction of Examples 1 and 5 and taken together with Table 1 depcit thestarting materials and products obtained thereby.

                  TABLE I                                                         ______________________________________                                         ##STR8##                                                                     Ex.                                                                           No.  XX.sup.1                                                                             X.sup.2                                                                              Y    A    A.sup.1                                                                            R.sup.1                                                                              R.sup.2 n                                                                          Z                               ______________________________________                                         8   Cl H   CF.sub.3                                                                             S    Cl   SH   H      H  1 CO.sub.2 Me                      9   Cl H   CF.sub.3                                                                             NH   Cl   NH.sub.2                                                                           H      H  1 CO.sub.2 Me                     10   Cl H   CF.sub.3                                                                             O    OK   Cl   H      H  2 CO.sub.2 H                      11   Cl H   CF.sub.3                                                                             O    OK   Br   H      H  3 CO.sub.2 Et                     12   Cl H   CF.sub.3                                                                             O    OK   Br   CH.sub.2 φ                                                                       H  1 CO.sub.2 Me                     13   Cl H   Cl     O    OK   Br   CH.sub.2 φ                                                                       H  1 CO.sub.2 Me                     14   Cl H   Cl     O    OK   Br   H      H  1 CO.sub.2 - .sub.-t-Bu           ______________________________________                                    

EXAMPLE 152-Chloro-4-trifluoromethyl-3'-(1-carboethoxy)iso-propoxycarbonyl-4'-nitrodiphenylether

2-Chloro-4-trifluoromethyl-3'-carboxy-4'-nitrodiphenylether (9.04 g.)and anhydrous potassium carbonate (6.91 g.) in DMSO (30 ml.) were heatedto 75° C. and ethyl α-bromoisobutyrate (4.9 g.) in DMSO (10 ml) wasadded and heating continued for 2 hours at 80°-82° C., at which pointadditional ethyl α-bromoisobutyrate (0.5 g.) was added. After twoadditional hours of heating, the mixture was cooled, and diluted withether. The ether solution was washed with 5% H₂ SO₄, and 1% NaOHsolutions, dried over magnesium sulfate, filtered through activatedsilica gel, and thoroughly stripped, finally at 0.5 mm/60°-65° C. toremove unreacted bromoester. The residue solidified to a yellow powderwhich was recrystallized from hexane to afford the desired ester, yield1.8 g., m.p. 92°-94.5° C. Found C, 50.15; H, 3.54; N, 2.89; Cl, 7.54; F,11.85. C₂₀ H₁₇ ClF.sub. 3 NO₇ requires C, 50.45; H, 3.60; N, 2.94; Cl,7.45; F 11.98.

EXAMPLE 162-Chloro-4-trifluoromethylphenyl-3'-[1-(carbo(2-methoxy)ethoxy)ethoxycarbonyl]-4'-nitrophenylether

A suspension of 2-chloro-4-trifluoromethyl-3'--carboxy-4'-nitrodiphenylether (7.1 g.) in thionyl chloride (2.5 g.) isheated for 1 hour at 110° C. then excess thonyl chloride stripped offunder reduced pressure. 2-Methoxyethanol (40 ml.) is added and themixture heated briefly to 95° C. to form a solution. Excess reagent isremoved under reduced pressure and the residue taken up in ether and thesolution washed with water and potassium carbonate solution, dried,filtered through activated silica gel, and stripped to yield the desiredester (7.5 g.) as a yellow oil. Found: C, 48.40; H, 3.13; Cl, 8.01; F,12.13; N, 3.62. C₁₉ H₁₅ ClF₃ NO₈ requires C, 47.76; H, 3.16; Cl, 7.42;F, 11.93; N, 2.93.

EXAMPLE 172-Chloro-4-trifluoromethyl-3'-(carbotrif1uoroethoxy)-methoxycarbonyl-4'-nitrodiphenylether.

This compound is prepared from2-chloro-4-tri-fluoromethyl-3'-(carboxymethoxycarbonyl)-4'-nitrodiphenylether and trifluoroethanol followingsubstanta11y the procedure ofExample 16.

EXAMPLE 182-Chloro-4-trifluoromethyl-3'-carbomethoxymethoxy-carbonyl-4'-nitrodiphenylether.

The potassium salt of2-chloro-4-trifluoromethyl-3-carboxy-4'-nitrodiphenyl ether is preparedby dissolving the acid in methanol and adding an equivalent amount ofpotassium hydroxide in methanol and evaporating the methanol. Thepotassium salt is dissolved in dry dimethyl formamide and methylα-bromoacetate (14.3 grams; 0.09375 mole) is added. The reaction mixtureis heated to 120° for 4 hours. The reaction mixture is added to dilutehydrochloric acid and extracted with hexane. The hexane solution iswashed until neutral and then filtered through activated silica gel. Thesolvent is removed to afford 16 grams of2-chloro-4-trifluoro-methyl-3'-carbomethoxymethoxycarbonyl-4'-nitrodiphenyether. m.p. 97°-98° C.

EXAMPLE 192-Chloro-4-trifluoromethylphenyl-3'-(carboallyloxy-methoxycarbonyl)-4'-nitrophenylether.

To a mixture of2-chloro-4-trifluoromethylphenyl-3'-carboxymethoxycarbonyl-4'-nitrophenylether (10.5 grams and potassium carbonate (4.1 gram) indimethylsulfoxide (30 milliliters) is added allyl bromide (3.0 gram) at25° C. The temperature increases to 32° C. and a yellow mixture isformed. A sample tested on thin layer chromatography shows a singlespot. The yellow mixture is diluted with 300 milliliters of water andextracted with 2×200 milliliter portions of ether. The ether extract iswashed with 100 milliliters of 5% potassium carbonate solution. Theether solution is dried over magnesium sulfate, filtered throughactivated silica gel and the ether removed to afford 10.3 grams ofyellow oil which solidifies. The solid is recrystallized from hexane toafford substantially pure2-chloro-4-trifluoromethylphenyl-3'-(carboallyloxymethoxycarbonyl)-4-nitrophenylether, m.p. 51°-53° C. Found C, 49.94; H, 2.86; Cl, 7.97; F, 12.49; N2.99; Cl₁₉ H₁₃ ClF₃ NO₄ requires C, 49.63; H, 2.85; Cl, 7.71; F, 12.40;N, 3.05.

EXAMPLE 202-Chloro-4-trifluoromethylphenyl-3'-(N-dimethyl)carbamylmethoxycarbonyl]-4'-nitrophenylether

To a well stirred mixture of an aqueous solution of dimethylamine (40%aqueous; 20 milliliters) and diethyl ether (100 milliliters) is addeddropwise2-chloro-4-trifluoromethylphenyl-3'-chlorocarbonylmethoxycarbonyl-4'-nitrophenylether. The aqueous phase becomes clear yellow. The reaction mixture isstirred for 20 minutes, the aqueous phase discarded and the yellow ethersolution is washed with 5% sulfuric acid and then a 5% potassiumcarbonate solution. The ether solution is dried over magnesium sulfateand filtered through activated silica gel. A precipitate forms whichafter standing and cooling is collected. The filtrate is stripped andthe crystals which form are collected and combined with the first cropto afford 4.3 grams of substantially pure2-chloro-4-trifluoromethylphenyl-3-[(N-dimethyl)carbamylmethoxycarbonyl]-4-nitrophenyl ether, m.p.108.5°-110° C. Found C, 48.43; H, 3.07; Cl, 8.29; F, 13.27; N, 6.22. C₁₈H₁₄ ClF₃ N₂ O₆ requires C, 48.38; H, 3.16; Cl, 7.94; F, 12.76; N, 6.27.

EXAMPLE 21 2,4-Dichloro-3'-carbomethoxymethoxycarbonyl-4'-nitrodiphenylether

A mixture of 2,4-dichloro-3-carboxy-4'-nitrodiphenyl ether (14.8 grams),potassium carbonate (8.2 grams) and dimethyl sulfoxide (30 milliliters)is warmed to 50° C. and then cooled to 33° C. at which point methylbromoacetate is added dropwise The reaction temperature increases to 45°C. The reaction mixture is stirred for an additional hour and then etherand water is added. The ether solution is washed with 5% sulfuric acid,5% sodium carbonate solution and 10% sodium hydroxide solution thendried over magnesium sulfate, filtered through activated silica gel andstripped to afford 14.5 grams of a yellow green oil. The oil isdissolved in 300 milliliters of isopropanolat 35° C. After cooling,crystals are collected and dried to afford 11.5 grams of2,4-Dichloro-3'-carbomethoxy-methoxycarbonyl-4'-nitrodiphenyl ether asyellow white needles m.p. 53°-55.5° C. Found C, 47.80; H, 2.64; Cl,18.10; N, 3.72; 0, 27.13. C₁₆ H.sub. 11 Cl₂ NO₇ requires C, 48.02; H,2.77; Cl, 17.72; N, 3.50; 0, 27.99.

EXAMPLE 22 Sodium salt of2-Chloro-4-trifluoromethyl-3'-(carboxy-methoxycarbonyl)-4'-nitrodiphenylether

To a suspension of2-chloro-4-trifluoromethyl-3'-(carboxymethoxycarbonyl)-4'-nitrodiphenylether (2.1 g.) in water (1,000 ml.) s slowly added dropwise over a 90minute period a solution of sodium hydroxide (9.5 ml. of 0.5 N dilutedto 50 ml.). The reaction mixture is stirred for an additional 90 minutesand then filtered to remove undissolved starting materials. The water isremoved under high vacuum at 30° C.-40° C. to afford 1.0 g. of2-chloro-4-trifluoromethyl-3'-(carboxymethoxycarb-onyl)-4'-nitrodiphenylether, sodium salt.

(a) By following substantially the procedure described in Example 22 andby substituting for the sodium hydroxide recited therein an equal molarquantity of potassium hydroxide there is obtained 1.2 g. of thepotassium salt of2-chloro-4-trifluoromethyl-3'-(carboxymethoxycarbonyl)-4'-nitrodiphenylether.

EXAMPLE 23 Lithium salt of2-Chloro-4-trifluoromethyl-3'-(carboxy-methoxycarbonyl)-4'-nitrodiphenylether

To a solution of2-chloro-4-trifluoromethyl-3'-(carboxymethoxycarbonyl)-4'-nitrodiphenylether (2.1 g. 0.005 mole) in diethyl ether (100 ml.) under nitrogen isadded n-butyl lithium solution (2.6 cc of a 1.9M solution; 0.0049 mole).The solution turns clear red. After 30 minutes of stirring the solutiondarkens. The reaction mixture is stirred overnight at room temperature.The solvent is removed to afford 2.4 g. of lithium salt of2-chloro-4-trifluoromethyl-3'-(carboxy-methoxycarbonyl)-4'-nitrodiphenylether as a crystalline brown solid.

EXAMPLE 242,4-Dichloro-3'-[1-(methoxycarbonyl)ethoxycarbonyl]-4'-nitrodiphenylether

To a solution of 2,4-dichloro-3'-carboxy-4'-nitrodiphenyl ether (8.88g.; 0.03 moles) in dimethylsulfoxide (30 ml.) is added potassiumcarbonate (8.29 g.; 0.06 mole). The mixture is heated to 70° C. for 5minutes and then cooled to 20° C. is added methyl α-bromo-proionate(5.01 g.; 0.03 moles) in dimethyl sulfoxide (5 ml.). After stirring thereaction mixture at room temperature for 90 minutes, it is diluted withether (200 ml.) and washed with water (100 ml.). The ether phase iswashed with 5% sulfuric acid and then 10 ml. of 5% sodium hydroxide. Theether solution is dried over magnesium sulfate and then filtered throughBio-sil. Removal of the ether affords 9.9 g. of2,4-dichloro-3'-[1-(methoxycarbonyl)ethoxycarbonyl]-4'-nitrodiphenylether as a yellow oil.

EXAMPLE 252-Chloro-4-trifluoromethyl-3'-[α-(methoxycarbonyl)-'-(phenyl)ethoxycarbonyl]-4'-nitrodiphenylether

To a stirred mixture of2-chloro-4-trifluoromethyl-3'-carboxy-4'-nitrodiphenyl ether (10.85 g.;0.03 moles) in methylethyl ketone (30 ml.) is added potassium carbonate(8.3 g.; 0.06 moles). An immediate reaction with gas evolution occursleaving a paper-like mass. After warming for 15 minutes at 60° C. themixture is cooled and methyl α-bromo-α-benzyl acetate (7.3 g.; 0.03moles) is added. The emulsion is very thick and an additional 80 ml. ofmethylethyl ketone s added. The reaction mixture is allowed to standovernight and then stirring is continued. An additional 200 ml. ofmethylethyl ketone is added and the reaction mixture is heated to 60° C.for 3 hours. The reaction mixture is cooled and diluted with diethylether (200 ml.). The ether solution is washed with water (200 ml.) andthen with 5% sulfuric acid and, finally, with 5% potassium carbonate.The ether solution is dried over molecular sieves. The ether solution isfiltered through activated silica gel and the ether removed to afford8.3 g. of a yellow oil. Thin layer of chromatography indicates asubstantial amount of unreacted ester. The yellow oil is diluted withmethylethyl ketone (70 ml.) and an additional quantity of thenitrodiphenyl ether (7.2 g.; 0.02 moles) and potassium carbonate (3.4g.; 0.02 moles) is added and the mixture heated to reflux and refluxingis continued overnight. The product is extracted with ether and theether solution is washed with water, 5% sulfuric aoid and, finally, 5%potassium carbonate solution. The ether solution is dried over magnesiumsulfate, filtered through activated silica gel and the ether removed toafford 1.9 g. of2-chloro-4-trifluoro-methyl-3'-[α-(methoxycarbonyl)-α-(phenyl)ethoxyocarbonyl]-4'-nitrodiphenyl ether.

EXAMPLE 26 2-Chloro-4-trifluoromethyl-3'-[α--(methoxycarbonyl)α-(phenyl)methoxycarbonyl]-4'-nitrodiphenyl ether

To a mixture of 2-chloro-4-trifluoromethyl-3'-carboxy-4'-nitrodiphenylether (7.23 g.; 0.02 moles) methylethyl ketone (25 ml.) is addedpotassium carbonate (5.52 g.; 0.04 moles). An immediate reaction occurswith gas evolution. An additional 100 ml. of methylethyl ketone is addedfollowed by the addition of methyl α-bromophenyl acetate (4.58 g.; 0.02moles). The reaction mixture is stirred for 90 minutes and allowed tostand overnight at room temperature. Stirring is continued for anadditional 4 hours at room temperature and then the reaction mixture isheated to 65° C. for 3 hours. The reaction mixture is cooled and diethylether (300 ml.) is added. The ether solution is washed with water; 5%sulfuric acid and, finally, a 5% potassium carbonate solution. The etherphase is dried over molecular sieves, filtered through activated silicagel and the ether removed to afford 8.5 g. of2-chloro-4-trifluoromethyl-3'-[α-(methoxycarbonyl)-α-(phenyl)metho -4'-nitrodiphenyl ether as a yellow solid. Recrystallization fromisopropanol affords 5.0 g. of fluffy white crystals, m.p. 114°-117° C.

EXAMPLE 272-Chloro-4-trifluoromethyl-3'-[(methoxycarbonyl)methylthiocarbonyl]-4'-nitrodiphenylether

2-Chloro-4-trifluoromethyl-3'-carboxy-4'-nitrodi-phenyl ether (12.6 g.;0.03 moles) and thionyl chloride (4.2 g.; 2.25 moles) is stirred andheated in a bath at 100° C. The mixture melts and heating is continuedat 100° C. for an additional hour. An additional 2 g. of thionylchloride is added and the mixture heated for 30 additional minutes. Thereaction mixture is allowed to stand overnight at room temperature andreheated for 2 hours. The excess thionyl chloride is removed undervacuum and chlorine and oil bath at 100° C. The dark brown oil is coldand diluted with diethyl ether (50 ml.). To this dark solution is addedethyl 2-mercaptoacetate (3.7 g.). The reaction mixture is stirred for 2hours at room temperature and then allowed to stand for 9 days(fortitutious). The mixture is then diluted with diethyl ether andwashed in water. The ether solution is washed with 5% sulfuric acidsolution and then a 5% potassium carbonate solution. The ether solutonis dried over magnesium sulfate and then filtered through activatedsilica gel. Removal of the ether affords 13.1 gram of product. Thismaterial is dissolved in diethyl ether (43 ml.) and enough hexane (85ml.) is added until hazy. This solution is then passed through activatedsilica gel and the solvent removed to afford 9.1 g. of2-chloro-4-tri-fluoromethyl-3'-[(methoxycarbonyl)methylthiocarbonyl]-4'-nitrodiphenylether as a red oil.

EXAMPLE 282-Chloro-4-trifluoromethyl-3-[α(ethoxycarbonyl)propoxycarbonyl]4'-nitrodiphenylether

A mixture of 2-chloro-4-trifluoromethyl-3-carboxy-4'-nitrodiphenyl ether(10.9 g.; 0.03 moles) in met ketone (50 ml.) is heated for 1 hour at60°-70° C. and then cooled. Ethyl 2-bromobutyrate (5.9 g.; 0.03 moles)is then added and the emulsion warmed to 50° C. for 2 hours. The mixtureis allowed to stand at room temperature overnight. Heating is resumed at60°-70° C. for an additional 4 hours. Ether (100 ml.) is added and theether solution washed with water, followed by 5% sulfuric acid solutionand, finally, with a 5% potassium carbonate solution. The ether is driedover magnesium sulfate and the ether solution is filtered throughactivated silica gel. The ether is removed to afford 6.2 g. of2-chloro-4-trifluoromethyl-3-[α(ethoxy-carbonyl)propoxycarbonyl]4'-nitro-diphenylether. The material is dissolved in hexane (except for some small amountabout 0.3 g. of orange oil) and the hexane decanted and removed toafford 5.6 g. of product. This material is redissolved in hexane andpassed through 40 g. of activated silica gel in hexane. Three cuts weretaken and the last two combined and the hexane removed to afford 2.5 g.of product as a yellow oil.

EXAMPLE 29 2-Chloro-4-trifluoromethyl-3-[N-(1-carboethoxyethyl)carboamyl]-4'-nitrodiphenyl ether

2-Chloro-4-trifluoromethyl-3'-carboxy-4'-nitrodiphenyl ether (0.04moles) and thionyl chloride (5.4 g.; 0.045 moles) are mixed together andrefluxed for two hours. 100 ml. of diethyl ether are added to thereaction mixture. This was then added dropwise to a mixture of ethylL-alanine hydrochloride (6.1 g.; 0.04 moles) and 2,6-lutidine (8.51 g.;0.08 moles) dissolved in 25 ml. of diethyl ether. The resultant red andblack solution was then stirred at room temperature overnight. The blacksolution is diluted with diethyl ether and then washed with water. Theether solution is then washed in 5% sulfuric acid followed by 5%potassium carbonate solution. The ether is dried over magnesium sulfateand filtered through activated silica gel. Removal of the ether affordsa black oil which soon solidifies. The solid is dissolved in hot hexane.The hexane is decanted and allowed to cold. The residual oil isextracted with hexane and the hexane extracts placed in a refrigerator.The first hexane extract affords 0.06 g. of product having a meltingpoint of 45°-47° C. The second extract affords a red black solidglass-like material, 3.9 g. having a melting point of 40°-49° C.

EXAMPLE 302-Chloro-4-trifluoromethyl-3'-[α-(ethoxycarbonyl)isobutoxycarbonyl]-4'-nitrodiphenylether

2-Chloro-4-trifluoromethyl-3'-carboxy-4'-nitrodi-phenyl ether (14.5 g.;0.04 moles) is dissolved in dimethyl sulfoxide (40 ml.). Potassiumcarbonate (11.0 g.; 0.08 moles) is added to this mixture. The reactionmixture is then heated to 60° C. The reaction mixture is cooled to roomtemperature and ethyl 2-bromo-3-methyl-butyrate (8.4 g.; 0.04 moles) indimethyl sulfoxide (10 ml.) is then added. The reaction mixture isstirred at room temperature and let stand. The reaction mixture isextracted with diethyl ether and the ether solution washed successivelywith water, 5% sulfuric acid solution and 5% potassium carbonatesolution. The ether solution is dried over magnesium sulfate andfiltered through activated silica gel. Removal of the ether affords 4.6g. of 2-chloro-4-trifluoromethyl-3'-[α(ethoxycarbonyl)-iso-butoxycarbonyl]-4'-nitro-dip ether.

EXAMPLE 312-chloro-4-trifluoromethyl-3'-[1-(aminocarbonyl)ethoxycarbonyl]-4'-nitrodiphenylether

2-chloro-4-trifluoromethyl-3'-carboxy-4'-nitrodi-phenyl ether (30.0 g.)is dissolved in dimethyl sulfoxi (30 ml.) and heated to 80° C. Potassiumcarbonate (12.6 g.) is then added. Foaming occurs and when the foamingceases the mixture is cooled in an ice bath to 38° C.α-Bromopropionamide (13.9 g.) is added. The reaction mixture is heatedfor 11/2 hours at 95° C. The reaction mixture is diluted with ether andthe ether extract is washed successively with water, 1% sodium hydroxidesolution and 5% sulfuric acid. The ether is removed and the residuecrystallized from toluene. The toluene solution is filtered crystalsform but are not the desired amine. The filtrate is stripped to afford4.0 g of desired2-chloro-4-trifluoromethyl-3'-[1-(aminocarbonyl)ethoxycarbonyl]-4'-nitrodiphenylether

EXAMPLE 322-Chloro-4-trifluoromethyl-3'[9-(carboxy)ethoxycarbonyl]-'-nitrodiphenylether

2-Chloro-4-trifluoromethyl-3'-[1-(methoxycarbonyl)methoxycarbonyl]-4'-nitrodiphenylether of Example 5 (47.7 g.; 0.107 moles) is mixed together with-toluenesulfonic acid (1.0 gram), dioxane (180 ml.) and water (5 ml.).The reaction mixture is heated, with stirring, to reflux for 6 hours.The reaction mixture is diluted with 5% sulfuric acid and extracted withether. The ether extract is itself extracted with 1% sodium hydroxidesolution. This base extract is acidified with sulfuric acid andextracted with ether. The first ether extract is dried over magnesiumsulfate, filtered through activated silica gel and the ether removed toafford 12.3 g. of2-chloro-4-trifluoromethyl-3'[1(carboxy)ethoxycarbonyl]-4'-nitrodiphenylether.

EXAMPLE 33 Sodium salt of2-Chloro-4-trifluoromethyl-3'[1-(carb-oxy)ethoxycarbonyl]-4'-nitrodiphenylether

The acid of Example 32 (2.2 g.) is dissolved in methanol (20 ml.). Tothis solution is added a sodium methoxide (0.27 g.; 0.005 mole) inmethanol (20 ml.). The reaction mixture is stirred for 10 minutes andthe methanol removed. The product is extracted with ether and the etherremoved to afford 2.1 g. of the sodium salt of2-chloro-4-trifluoromethyl-3'[1-(carboxy)-ethoxycarbonyl]-4'-nitrodiphenylether.

EXAMPLE 34 Potassium salt of2-Chloro-4-trifluoromethyl-3'[1-(carboxy)ethoxycarbonyl]-4'-nitrodiphenylether

The product of Example 32 (2.2 g.) is dissolved in methanol. To thissolution is added a solution of potassium hydroxide (0.28 g.) inmethanol (20 ml.). The reaction mixture is stirred for 10 minutes andthe methanol removed under vacuum. The product is extracted with etherand the ether removed to afford 2.1 of2-chloro-4-trifluoromethyl-3'[1-(carboxy)ethoxycarbonyl]-4'-nitrodiphenyl ether, potassium salt, m.p. 100°-105° C.

EXAMPLE 352-Chloro-4-trifluoromethyl-3'-[α-(ethoxycarbonyl)-α-methylethoxycarbonyl]-4'-nitrodiphenylether

A mixture of2-chloro-4-trifluoromethyl-3'-chloro-carbonyl-4'-nitrodiphenyl ether (10g.); ethyl 3(3.5 g.) and lutidine (2.8 g.) in toluene (15 ml.) is heatedwith stirring to 55° C. Heating is continued for two days(fortitutious). The reaction mixture is diluted with water and extractedwith ether. The ether solution is washed with a 5% sodium carbonatesolution and then water. The ether solution is then dried over magnesiumsulfate filtered through charcoal and activated silica gel and thesolvent removed to yield 8.2 g. of2-chloro-4-trifluoro-methyl-3'-[α-(ethoxycarbonyl)-α-methylethoxycarbony 4'-nitrodiphenyl ether as an oil.

EXAMPLE 362-Chloro-4-trifluoromethyl-3'-(carboethoxybutoxycarb-onyl)-4'-nitrodiphenylether

2-Chloro-4-trifluoromethyl-3'-carboxy-4'-nitrodiphenyl ether (10.85 g,0.03 moles) is dissolved in methylethyl ketone (30 ml.) and potassiumcarbonate (8.3 g; 0.06 moles) added. A solid forms. Additional methylethyl ketone (40 ml) is added and the emulsion heated in an oil bath at100° C. and then cooled in an ice bath. Ethyl 5-bromovalerate (6.27 g;0.03 ml) is added and also additional methylethyl ketone (10 ml) tomaintain slurring. The reaction mixture is heated to 60° C. for 5minutes, cooled and stirred at room temperature for 2 hours at roomtemperature. The mixture is colored pinkpurple. The emulsion is dilutewith either and the ether solution washed with water, 5% sulfuric acidsolution and then 5% potassium carbonate. The ether solution is driedover magnesium sulfate and filtered through activated silica gel. Theether is removed to afford 8.0 g. of yellow oil NMR shows impurity ofethyl 5-bromovalerate which is removed by distillation. The residue is2.5 g of2-Chloro-4-trifluoromethyl-3'-(carboethoxybutoxycarbonyl)-4'-nitrodiphenylether. NMR and IR confirm product.

EXAMPLE 372-Chloro-4-trifluoromethyl-3'-carboethoxymethoxycar-bonyl-4'-nitrodiphenylether

To a 12 1, 4-necked round bottom flask is added2-chloro-4-trifluoromethyl-3'-carboxy-4'-nitrodiphenyl ether (2713 g;7.5 moles) in methylethyl ketone (MEK) (6.6 1) under a nitrogenatmosphere. Heated to 79° C. (collected 100 ml of MEK). Cooled to 40° C.and removed 3700 ml of solution. Added potassium carbonate (250 gl inabout 3 to 5 minutes --to fast as violent foaming occurred causing aloss of 2.5 to 3.1 of material. Added MEK (800 ml). Heated to 60° C. andcontinued addition of potassium carbonate (807 g; total 1057 g, 7.65moles). Stirred overnight at a temperature of about 40° C. Heated to 70°C. and added ethyl bromoacetate (1466 g; 8.25 moles) over a 21/2 hourperiod. The temperature was increased to distill MEK. (Removed 2200 mlover a 41/2 period). The heat was removed and stirring was continuedovernight at room temperature. The reaction mixture is washedsuccessively with water (4500 ml), (the water wash is extracted with 6pints of toluene) 10% sodium carbonate (2500 ml), brine (2500 ml) andwater (2500 ml). The MEK solution and toluene are combined, dried overmagnesium sulfate, filtered and stripped under vacuum to afford 3347 gof 2-Chloro-4-trifluoromethyl-3'-carboethoxymethoxycarbonyl-4'-nitroether m.p. 47°-52° C.

Other salts, esters, amides of the acid may be prepared by methodsdisclosed herein and by other methods known to those skilled in the artand include the alkali metal and alkaline earth metal salts, the mono-and dialkyl amines and the lower alkyl ester derivatives.

One skilled in the art will appreciate that the above examples aremerely illustrative and are capable of a wide variation and modificationwithout departing from the spirit of this invention as defined by thefollowing clams.

TEST PROCEDURE

This example shows the herbicidal activity of the diphenyl ethers of theinvention exhibited on the following representative species:

    ______________________________________                                                                Approximate                                                                   No. Seeds                                             ______________________________________                                        Monocots:                                                                             Barnyardgrass                                                                             (Echinochloa  25                                                              crusgalli)                                                        Downybrome  (Bromus tectorum)                                                                           20                                                  Foxtail     (Setaria spp) 25                                                  Johnsongrass                                                                              (Sorghum      25                                                              halepense)                                                        Nutsedge    (Cyperus       5                                                              esculentus)                                                       Wild Oat    (Avena fatua) 20                                          Dicots: Cocklebur   (Xanthium      3                                                              pensylvanicum)                                                    Marigold    (Tagetes spp) 15                                                  Morning-    (Ipomoea spp) 10                                                  glory                                                                         Tomato      (Lycopersicon 15                                                              esculentum)                                                       Velvetleaf  (Abutilon     15                                                              theophrasti)                                              ______________________________________                                    

The following test procedure is employed. Seeds of the above species areplanted in soil in trays (approx. 7"×10 1/2"×3"). For preemergencetests, the trays are sprayed with the test compound immediately afterplanting. For postemergence tests, the seeds are allowed to germinateand after growing in the greenhouse for two weeks, the growing plantsare treated with the test compound. The compound to be evaluated isdissolved in acetone or water and sprayed over the trays using a carriervolume equivalent to 50 gallons per acre at the rate of applictation (inpounds per acre, lb/A) specified in the table. About two weeks afterapplication of the test compound, the state of growth of the plants isobserved and the phytotoxic effect of each compound determined asfollows: each species is evaluated on a scale of 0-100 in which 0=noactivity and 100=total kill and the result for the monocots and dicotsseparately averaged. The following table sows the results obtained forthe compounds of the invention at 0.5 lb/A. and 2.0 lb/A. except asnoted*.

    ______________________________________                                        Diphenylethers - Herbicidal Activity                                          Rate 0.5 lb/A      Rate 2.0 lb/A                                              Ex.  Pre         Post      Pre      Post                                      No.  AM.sup.+                                                                              AD.sup.+                                                                              AM   AD   AM    AD   AM    AD                            ______________________________________                                         1   42      52      10   44   77    98   23    55                             2   62      58      38   93   93    98   57    96                             3   2       4       2    18   5     49   2     22                             4   2       42      33   94   0     20   20    96                             5   48      39      60   92   76    99   68    98                             6   45      58      43   92   83    100  50    98                            11   31      85      37   98   56    100  75    100                           15   42      76      18   80   75    97   25    96                            16   15      38      3    79   70    94   37    100                           *17  73      77      43   99   72    92   46    98                            18   55      55      52   100  94    99   75    100                           19   27      44      10   84   90    98   25    95                            20   25      44      2    54   58    82   17    72                            21   0       19      3    63   0     56   7     91                            22   38      46      25   89   88    89   70    100                           *22a 74      88      53   96   87    99   40    100                           *23  76      91      27   96   74    97   31    91                            24   10      4       7    56   7     67   13    80                            25   18      59      5    38   68    72   10    51                            26   34      76      0    24   23    57   0     18                            27   42      36      7    78   78    93   30    94                            28   60      99      42   99   75    100  67    100                           29   13      40      0    78   50    54   0     79                            30   22      92      3    59   40    100  12    79                            *32  79      84      28   99                                                  *33  64      48      20   98                                                  *34  62      58      22   100                                                 35   45      74      35   96   91    99   64    99                            37   48      66      34   95   86    100  58    99                            ______________________________________                                         *1.0 lb/A.                                                                    +AM = Average Monocot; AD = Average Dicot                                

    __________________________________________________________________________    DIPHENYLETHERS - PHYSICAL DATA                                                Example     Molecular  C found                                                                              H found                                                                             N found                                                                             Cl found                            #    m.p.   Formula    (reqd) (reqd)                                                                              (reqd)                                                                              (reqd)                              __________________________________________________________________________     1   25° C.                                                                        C.sub.20 H.sub.17 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                       50.13 (50.49)                                                                        3.51 (3.60)                                                                         2.87 (2.94)                                                                         7.38 (7.45)                          2   103.5-106° C.                                                                 C.sub.16 H.sub.7 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                        45.99 (45.79)                                                                        2.59 (2.16)                                                                         2.88 (3.34)                                                                         8.00 (8.45)                          3   69-79° C.                                                                     C.sub.19 H.sub.17 Cl.sub.2 N.sub.1 O.sub.7                                               51.87 (51.60)                                                                        3.87 (3.88)                                                                         3.65 (3.17)                                                                         16.50 (16.03)                        4   93-95° C.                                                                     C.sub.15 H.sub.9 Cl.sub.2 N.sub.1 O.sub.7                                                46.52 (46.65)                                                                        2.29 (2.35)                                                                         3.78 (3.63)                                                                         18.40 (18.36)                        5   Oil    C.sub.18 H.sub.13 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                       46.94 (48.29)                                                                        2.90 (2.93)                                                                         2.93 (3.13)                                                                         8.59 (7.92)                          6   Oil    C.sub.19 H.sub.15 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                       49.16 (49.39)                                                                        3.19 (3.27)                                                                         3.31 (3.03)                                                                         8.20 (7.68)                         11   Oil    C.sub.20 H.sub.17 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                       50.66 (50.49)                                                                        3.80 (3.60)                                                                         3.02 (2.94)                                                                         8.27 (7.45)                         15   92-94.5° C.                                                                   C.sub.20 H.sub.17 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                       50.15 (50.45)                                                                        3.54 (3.60)                                                                         2.89 (2.94)                                                                         7.54 (7.45)                         16   Oil    C.sub.19 H.sub.15 Cl.sub.1 F.sub.3 N.sub.1 O.sub.8                                       48.40 (47.76)                                                                        3.13 (3.16)                                                                         3.62 (2.93)                                                                         8.01 (7.42)                         17   Oil    C.sub.18 H.sub.10 Cl.sub.1 F.sub.6 N.sub.1 O.sub.7                                       43.78 (43.09)                                                                        2.02 (2.01)                                                                         2.79 (2.79)                                                                         7.04 (7.07)                         18   97-98° C.                                                                     C.sub.17 H.sub.11 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                       45.36 (47.07)                                                                        2.76 (2.56)                                                                         3.26 (3.23)                                                                         9.26 (8.17)                         19   51-53° C.                                                                     C.sub.19 H.sub.13 Cl.sub.1 F.sub.3 N.sub.1 O.sub.4                                       49.94 (49.63)                                                                        2.86 (2.85)                                                                         2.99 (3.05)                                                                         7.97 (7.71)                         20   108.5-110° C.                                                                 C.sub.18 H.sub.14 Cl.sub.1 F.sub.3 N.sub.2 O.sub.6                                       48.43 (48.38)                                                                        3.07 (3.16)                                                                         6.22 (6.27)                                                                         8.29 (7.94)                         21   53-55° C.                                                                     C.sub.16 H.sub.11 Cl.sub.2 N.sub.1 O.sub.7                                               47.80 (48.02)                                                                        2.64 (2.77)                                                                         3.72 (3.50)                                                                         18.10 (17.72)                       22   --     C.sub.16 H.sub.8 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7 Na                                     41.72 (43.51)                                                                        1.91 (1.83)                                                                         2.82 (3.17)                                                                         5.32 (8.03)                           22a                                                                              --     C.sub.16 H.sub.8 Cl.sub.1 F.sub.3 N.sub.1 O.sub.2 K.sub.1                                45.15 (41.98)                                                                        2.04 (1.76)                                                                         3.19 (3.06)                                                                         8.66 (7.74)                         23   --     C.sub.16 H.sub.8 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7 Li                                     45.65 (45.15)                                                                        2.88 (1.89)                                                                         2.80 (3.29)                                                                         7.99 (8.33)                         24   Oil    C.sub.17 H.sub.13 Cl.sub.2 N.sub.1 O.sub.7                                               49.17 (49.29)                                                                        3.09 (3.16)                                                                         3.58 (3.38)                                                                         17.74 (17.12)                       25   Oil    C.sub.24 H.sub.17 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                       55.29 (55.02)                                                                        3.41 (3.27)                                                                         2.83 (2.67)                                                                         7.27 (6.77)                         26   114-117° C.                                                                   C.sub.23 H.sub.15 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                       54.28 (54.18)                                                                        2.83 (2.96)                                                                         2.94 (2.75)                                                                         7.02 (6.96)                         27   Oil    C.sub.18 H.sub.13 Cl.sub.1 F.sub.3 N.sub.1 O.sub.6 S.sub.1                               46.33 (46.60)                                                                        2.72 (2.82)                                                                         2.98 (3.02)                                                                         8.43 (7.44)                         28   Oil    C.sub.20 H.sub.17 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                       52.28 (50.48)                                                                        3.85 (3.60)                                                                         3.01 (2.94)                                                                         7.65 (7.45)                         29   45-47° C.                                                                     C.sub.19 H.sub.16 Cl.sub.1 F.sub.3 N.sub.2 O.sub.6                                       49.08 (49.52)                                                                        3.06 (3.50)                                                                         5.24 (6.08)                                                                         11.89 (7.70)                        30   Oil    C.sub.21 H.sub.19 Cl.sub.1 F.sub.3 N.sub.1 O.sub.                                        50.40 (51.45)                                                                        3.82 (3.91)                                                                         3.14 (2.86)                                                                         9.16 (7.24)                         31   Oil    C.sub.17 H.sub.12 Cl.sub.1 F.sub.3 N.sub.2 O.sub.6                                       51.67 (47.18)                                                                        3.46 (2.80)                                                                         5.58 (6.47)                                                                         8.07 (8.19)                         32   Oil    C.sub.17 H.sub.11 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                       47.23 (47.08)                                                                        2.87 (2.56)                                                                         2.88 (3.23)                                                                         7.59 (8.17)                         33   105-110° C.                                                                   C.sub.17 H.sub.11 Cl.sub.1 F.sub.3 N.sub.1 O.sub.2 Na                                    44.27 (44.81)                                                                        2.14 (2.21)                                                                         3.29 (3.07)                                                                         7.42 (7.78)                         34   100-105° C.                                                                   C.sub.17 H.sub.11 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7 K                                     43.88 (43.28)                                                                        2.59 (2.14)                                                                         2.88 (2.97)                                                                         7.43 (7.51)                         35   Oil    C.sub.20 H.sub.17 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                       53.96 (50.49)                                                                        3.99 (3.60)                                                                         3.05 (2.94)                                                                         7.23 (7.45)                         36   Oil    C.sub.21 H.sub.19 Cl.sub.1 F.sub.3 N.sub.1 O.sub.7                                       53.46 (51.49)                                                                        4.16 (3.91)                                                                         2.71 (2.86)                                                                         7.38 (7.24)                         __________________________________________________________________________

The following is a listing of some of the preferred products of thisinvention.

    ______________________________________                                         ##STR9##                                                                     Ex-                                                                           am-                                                                           ple  X     X.sup.2                                                                              X.sup.1                                                                           Y    R.sup.1                                                                              R.sup.2 n                                                                          Z                                      ______________________________________                                         1   Cl    CF.sub.3                                                                             H   O    H      H 1  CO.sub.2 - .sub.-t-Bu                   2   Cl    CF.sub.3                                                                             H   O    H      H 1  CO.sub.2 H                              3   Cl    Cl     H   O    H      H 1  CO.sub.2 - .sub.-t-Bu                   4   Cl    Cl     H   O    H      H 1  CO.sub.2 H                              5   Cl    CF.sub.3                                                                             H   O    Me     H 1  CO.sub.2 Me                             6   Cl    CF.sub.3                                                                             H   O    Me     H 1  CO.sub.2 Et                            11   Cl    CF.sub.3                                                                             H   O    H      H 3  CO.sub.2 Et                            15   Cl    CF.sub.3                                                                             H   O    Me     Me 1 CO.sub.2 Et                            16   Cl    CF.sub.3                                                                             H   O    H      H 1  CO.sub.2 CH.sub.2 CH.sub.2 OMe         17   Cl    CF.sub.3                                                                             H   O    H      H 1  CO.sub.2 CH.sub.2 CF.sub.3             18   Cl    CF.sub.3                                                                             H   O    H      H 1  CO.sub.2 Me                            19   Cl    CF.sub.3                                                                             H   O    H      H 1  CO.sub.2 CH.sub.2 CHCH.sub.2           20   Cl    CF.sub.3                                                                             H   O    H      H 1  CONMe.sub.2                            21   Cl    Cl     H   O    H      H 1  CO.sub.2 Me                            22   Cl    CF.sub.3                                                                             H   O    H      H 1  CO.sub.2 Na                             22a Cl    CF.sub.3                                                                             H   O    H      H 1  CO.sub.2 K                             23   Cl    CF.sub.3                                                                             H   O    H      H 1  CO.sub.2 Li                            24   Cl    Cl     H   O    Me     H 1  CO.sub.2 Me                            25   Cl    CF.sub.3                                                                             H   O    CH.sub.2 C.sub.6 H.sub.5                                                             H 1  CO.sub.2 Me                            26   Cl    CF.sub.3                                                                             H   O    C.sub.6 H.sub.5                                                                      H 1  CO.sub.2 Me                            27   Cl    CF.sub.3                                                                             H   S    H      H 1  CO.sub.2 Et                            28   Cl    CF.sub.3                                                                             H   O    Et     H 1  CO.sub.2 Et                            29   Cl    CF.sub.3                                                                             H   NH   Me     H 1  CO.sub.2 Et                            30   Cl    CF.sub.3                                                                             H   O     .sub.-i-Pr                                                                          H 1  CO.sub.2 Et                            31   Cl    CF.sub.3                                                                             H   O    Me     H 1  CONH.sub.2                             32   Cl    CF.sub.3                                                                             H   O    Me     H 1  CO.sub.2 H                             33   Cl    CF.sub.3                                                                             H   O    Me     H 1  CO.sub.2 Na                            34   Cl    CF.sub.3                                                                             H   O    Me     H 1  CO.sub.2 K                             35   Cl    CF.sub.3                                                                             H   O    Me     H 2  CO.sub.2 Et                            36   Cl    CF.sub.3                                                                             H   O    H      H 4  CO.sub.2 Et                            ______________________________________                                    

What is claimed is:
 1. A process for preparing a compound of the formula##STR10## wherein X is hydrogen, halo, trihalomethyl, alkyl, cyano ornitro; X¹ is hydrogen, halo or trihalomethyl, X² is trihalomethyl orhalo; R¹ and R² are the same or different radicals selected fromhydrogen, lower alkyl or mononuclear aryl lower alkyl; n is an integerof from 1 to 5; and Z is carboxy, amino, monoalkylamino, or dialkylaminoand when Z is carboxy, the agronomically acceptable salts, esters andamides thereof, which comprises treating a compound of the formula:##STR11## wherein X, X¹ and X² are as defined above and M is a cationderived from al alkali metal or alkaline earth metal base, with acompound of the formula; Halo(CR¹ -R²)_(n) Z, wherein R¹, R², n and Zare as defined above and halo is chloro, bromo or fluoro in the presenceof an inert solvent at a temperature in the range of from about 20° toabout 150° C. followed by nitration at a temperature in the range offrom about 20° to about 200° C.
 2. A process for preparing a diphenylether of the graphic formula: ##STR12## wherein X is hydrogen orhalogen; Y is hydrogen, halogen, cyano, trifluoromethyl, or an alkylradical containing from 1 to 4 carbon atoms; Z is oxygen or sulfur; R isa methylidene or monosubstituted methylidene, whrein the substituent isselected from the group consisting of alkyl, oxoalkyl and hydroxyalkylradicals containing from 1 to 4 carbon atoms; and R¹ is hydrogen, or analkyl radical containing from 1 to 8 carbon atoms, a cycloalkyl radicalcontaining from 3 to 8 carbon atoms, an agronomically acceptablecationic salt, phenyl, or mono-,di-, or tri-substituted pehnyl, saidsubstituents being selected from the group consisting of halogen, alkylor alkoxy radicals containing from 1 to 10 carbon atoms, cyano, nitro,and trifluoromthyl; which comprises the sequential steps of:(a) reactinga diphenyl ether of the graphic formula: ##STR13## wherein X and Y areas defined above, with an inorganic alkali metal base to form thecorresponding acid salt; (b) reacting the acid salt of step (a) with anα-halocar-boxylic acid ester of the graphic formula: ##STR14## wherein Rand Z are as defined above; R¹ is an alkyl radical containing from 1 to8 carbon atoms, a cycloaklyl radical containing from 3 to 8 carbonatoms, phenyl, or mono-, di-, or trisubstituted phenyl, saidsubstituents being selected from the group consisting of halogen, alkylor alkoxy radicals containing from 1 to 10 carbon atoms, cyano, nitro,and trifluormethyl; and Hal is selected from the group consisting ofchlorine, bromine and iodine, to form the corresponding ester; and (c)nitrating the ester product of step (b) with a nitrating agent selectedfrom the group consisting of nitric acid; mixtures of nitric acid andsulfuric acid; mixtures of potassium nitrate and sulfuric acid; andmixtures of nitric acid, sulfuric acid, and acetic anhydride, thereby toform a diphenyl ether represented by graphic Formula I.
 3. The processof claim 2 wherein the inorganic alkali metal base is an alkali metalhydroxide.
 4. The process of claim 2 wherein the nitrating agent is amixture of nitric acid, sulfuric acid and acetic anhydride.